RU2461029C2 - Reflecting article - Google Patents

Abstract

FIELD: physics.

SUBSTANCE: reflecting article includes a transparent substrate, having a first and a second base surface; a base layer formed on top of at least part of the second base surface; a primary reflecting coating formed on top of at least part of the base layer; an inorganic protective coating consisting of silicon dioxide, aluminium oxide or a mixture of silicon dioxide and aluminium oxide, formed on top of at least part of the primary reflecting coating; as well as a top coating which contain zinc stannate, formed between the primary reflecting coating and the inorganic protective coating. The base layer contains titanium dioxide with thickness of 1-3 nm.

EFFECT: higher reflecting power and longer operating life.

15 cl, 7 dwg

Description

FIELD OF THE INVENTION

The present invention relates mainly to a coated base layer and, in one particular embodiment, to a coated glass substrate used, in particular, to reflect electromagnetic radiation, such as electromagnetic solar radiation.

State of the art

With the rising cost of fossil fuels, solar energy is becoming more affordable for industry and an economically viable source of energy. One well-known option is to use mirrors to concentrate solar energy to generate electricity. Mirrors with a high reflectivity of solar radiation, are used for devices "thermal energy from concentrated sunlight" (CSTP). There are mirrors with different geometries that are used in this technical field. In one traditional system, curvilinear parabolic solar mirrors are used to concentrate solar energy on tubes located along the focal line. The heat transfer medium in the tubes transfers the absorbed thermal energy to the generator unit, where it is used to generate electricity. Another traditional system uses a solar tower, in which several flat solar mirrors direct solar energy to a specific location in the tower. The heat generated by focused solar energy is transferred to a working fluid, such as sodium, with the heated working fluid used to generate energy.

Another area of application for such mirrors is "concentrated photovoltaic cells" (CPV). In this application, mirrors focus or concentrate solar energy on highly efficient photovoltaic (PV) devices, and thus, the energy output in this device is improved.

In these known systems, it is desirable that the mirrors reflect as much solar energy as possible. In addition, it is desirable that the mirrors have as long a service life as possible in order to prevent frequent mirror replacement.

The traditional technology for the production of mirrors uses a wet chemical deposition method in which silver is deposited on a glass substrate from a solution of silver nitrate. The problem with such known systems is that the spent solution must be disposed of in an environmentally acceptable manner. Moreover, in such conventional systems, it is not possible to treat the coated article at high temperature (for example, for hardening, tempering or bending) after the silver layer has been deposited, since this will damage the silver layer. Although some conventional mirrors have a copper layer deposited by wet chemical deposition over a silver layer in order to slow down the corrosion of silver, such traditional copper layers cannot adequately protect the silver layer to allow the coated glass to heat to a softening temperature. In addition, a copper layer deposited by a wet chemical process is undesirable for environmental reasons, specifically because of the need to remove the wastewater from the wet chemical process.

Therefore, it would be advisable to create a reflective product and a method for producing a reflective product in which at least some of the problems inherent in such traditional products are eliminated or reduced.

SUMMARY OF THE INVENTION

The reflective article includes a transparent substrate having a first main surface and a second main surface. On top of at least part of the second main surface, a base layer is formed. A primary reflective coating is formed over the base layer. An inorganic protective coating is formed over at least a portion of the primary reflective coating. In one non-limiting embodiment, the base layer comprises an inorganic material, such as a transparent dielectric material.

Another reflective article includes a transparent glass substrate having a first main surface and a second main surface. On top of at least a portion of the second main surface, an inorganic base layer is formed which contains at least one metal oxide selected from alumina, titanium dioxide, zirconia, zinc oxide, zinc stannate, tin oxide, or mixtures thereof, or combinations thereof, and has a thickness in the range from 0.1 nm to 5 nm. At least a primary reflective coating is formed over the base layer, which contains at least one metal selected from platinum, iridium, osmium, palladium, aluminum, gold, copper, silver, or mixtures, alloys, or combinations thereof, and has a thickness in the range from 50 nm to 500 nm, and is opaque in the visible region of the spectrum. An anticorrosion coating is formed over at least a portion of the primary reflective coating, wherein the anticorrosion coating contains at least one metal or metal alloy, consisting of representatives of groups 2-16 of the Periodic Table of Elements, and has a thickness in the range of 20 nm up to 40 nm. A topcoat is formed over at least a portion of the anti-corrosion coating, the topcoat containing at least one layer containing a material selected from oxides, nitrides, oxynitrides, borides, fluorides, or metal carbides, and where the topcoat has a thickness in the range from 5 nm to 500 nm. An inorganic protective coating is formed over at least a portion of the topcoat, the protective coating comprising a material selected from silica, alumina, or a mixture of silica and alumina, and has a thickness in the range of 50 nm to 500 nm.

Additionally, the reflective article includes a transparent glass substrate having a first main surface and a second main surface. On top of at least part of the second main surface, a base layer is formed which comprises a titanium dioxide layer having a thickness in the range of 1 nm to 3 nm. On top of at least part of the base layer, a primary reflective coating is formed that contains a silver layer having a thickness in the range of 50 nm to 200 nm. An anti-corrosion coating is formed over at least a portion of the primary reflective coating, the anti-corrosion coating comprising a nickel-containing alloy having a thickness in the range of 20 nm to 40 nm. On top of at least a portion of the anticorrosion coating, an upper coating is formed which comprises a zinc stannate layer having a thickness in the range of 100 nm to 200 nm. An inorganic protective coating is formed over at least a portion of the top coating, the protective coating comprising a material selected from silica, alumina, or a mixture of silica and alumina, and has a thickness in the range of 50 nm to 200 nm.

A method of obtaining a reflective product includes the steps of:

obtaining a transparent base layer having a first main surface and a second main surface; depositing an inorganic base layer over at least a portion of the second main surface; the deposition of at least one primary reflective coating, which is opaque in the visible region of the spectrum, over at least at least part of the base; and depositing an inorganic protective coating over at least a portion of the primary reflective coating.

Brief Description of the Drawings

The invention will be described with reference to the following figures of the drawings, in which similar parts are everywhere denoted by the same reference numerals.

On figa shows a side view in section (not to scale) of a reflective product, including signs of the invention;

on figv shows a side view in section (not to scale) of another reflective product, including signs of the invention;

on figs shows a side view in section (not to scale) additional reflective products, including signs of the invention;

figure 2 shows a side view in section (not to scale) of another reflective product of the invention;

figure 3 is a side view in section (not to scale) of an additional reflective product of the invention;

4 is a side view in section (not to scale) of an additional reflective product of the invention; and

figure 5 shows a side view (not to scale) of the reflective product of the invention, mounted on a frame.

Description of preferred embodiments of the invention

Used in the invention of spatial terms or terms indicating directions, such as “left”, “right”, “internal”, “external”, “above”, “below” and the like, have the meaning shown in the figures of the drawings. However, it should be understood that the invention may allow various alternative orientations and, accordingly, such terms should not be construed as limiting. In addition, it should be understood that all numbers used in the description and claims expressing dimensions, physical characteristics, technological parameters, quantities of components, reaction conditions and the like can be modified in all cases using the term “approximately”. Therefore, unless indicated to the contrary, the numerical values set forth in the following description and claims may vary depending on the desired properties that can be obtained using the present invention. At a minimum, but not as an attempt to limit the use of the doctrine of equivalents to the scope of the claims, each numerical value should be construed, at least in light of the number of significant figures given, using traditional rounding techniques. Moreover, all the ranges described in the description should be understood as including the initial and final values of the range and any, and all sub-ranges assigned to this category. For example, the formulated range “from 1 to 10” should be considered as including any and all subranges between (and inclusive) the minimum value of 1 and the maximum value of 10; that is, all subranges, starting from a minimum value of 1 or more and ending with a maximum value of 10 or less, for example from 1 to 3.3, from 4.7 to 7.5, from 5.5 to 10, and the like. In addition, the terms used in the invention “formed over (over)”, “deposited over (over)”, or “obtained over (over)” mean formed, deposited or obtained on the surface, but not necessarily in direct contact with the surface. For example, a coating layer “formed over” a base layer does not exclude the presence of one or more other coating layers or films of the same or different composition located between the formed coating layer and the substrate. As used herein, the terms “polymer” or “polymer” include oligomers, homopolymers, copolymers and terpolymers, for example polymers formed from two or more types of monomers or polymers. The terms “visible range” or “visible light” refer to electromagnetic radiation having a wavelength in the range of 380 nm to 780 nm. The terms “infrared region” or “infrared radiation” refer to electromagnetic radiation having a wavelength in the range of more than 780 nm and up to 100,000 nm. The terms "ultraviolet region" or "ultraviolet radiation" means electromagnetic radiation having a wavelength in the range from 100 nm to less than 380 nm. In addition, all documents, such as (but not limited to) granted patents and patent applications, referred to in the invention, should be construed as fully "incorporated into the present invention as references". In addition, parameters such as “visible light transmission” and “visible light reflection” and the like are determined using conventional methods. Those skilled in the art can understand that characteristics such as transmitting visible light or reflecting visible light can vary depending on physical dimensions, such as the thickness of the test article. Therefore, a design comparison with the present invention should be carried out at an equivalent thickness.

For the purpose of subsequent discussion, the invention will be considered with reference to the use of a reflective product for reflecting electromagnetic radiation, such as (but not limited to) a solar mirror for reflecting electromagnetic solar radiation. The term “solar mirror” as used in the invention refers to any product arranged to reflect electromagnetic solar radiation, such as visible and / or infrared and / or ultraviolet radiation, for example, for use in solar energy concentration systems. However, it should be understood that the invention is not limited to use in solar mirrors, it can be applied in practice in other fields, such as (but not limited to) laminated or non-laminated household and / or industrial mirrors, or reflectors for high-performance optical systems (for example, video projectors or optical scanners), only a few areas are named. Therefore, it should be understood that the specifically described embodiments are provided only to explain the general concept of the invention and that the invention is not limited to these specifically described embodiments.

In a broad aspect, the reflective article of the invention includes at least some of the following components:

(1) a photoconductive substrate or an overlapping layer having a small absorption of solar radiation in the region (s) of the electromagnetic spectrum in which reflection from the product is required,

(2) one or more primary reflective layers having a high reflectivity of solar radiation in areas of the electromagnetic spectrum in which reflection is required,

(3) an optional “primer” or “blocking” or “barrier” layer (s) that can help maintain the reflective characteristics of the reflective layer (s) and / or improve the adhesion of adjacent components,

(4) one or more optional secondary reflective layers, such as additional metal, semiconductor, dielectric and / or composite layers, which can enhance the reflectivity of the product in some or all of the required wavelength ranges, and / or can protect the primary reflective layer (layers ), and / or to prevent the diffusion of chemical particles between the layers and / or the base layer / overlapping layers,

(5) an optional corrosion preventing layer (s),

(6) an optional tread layer (s) containing materials that are more susceptible to corrosion than materials containing components 2, 3 and / or 4,

(7) an optional layer (s) of materials (e.g. metal or metal alloys) that are corrosion resistant and / or form passivating layers that prevent the chemical interaction / reaction of chemically active environmental particles with other components,

(8) an optional sealing layer (s) that protects the underlying layers (especially the reflective layer (s)) from exposure to hazardous environmental factors (e.g., air pollution, water, solids),

(9) an optional adhesive layer (s) that connects the product to optional underlying thin plates / layers / base layer / overlapping layers or other supporting structures,

(10) an optional polymer layer (s),

(11) optional additional thin plates / layers / base layer / overlapping layers,

(12) an optional, maintenance free (e.g., hydrophilic and / or photocatalytic or hydrophobic) top side, and

(13) optional edge seals.

A non-limiting reflective product incorporating features of the invention is shown in FIG. 1A and will be described herein as sun mirror 1. This sun mirror 1 may have any desired reflectance or transmittance in the region (s) of interest within the electromagnetic spectrum (e.g. ultraviolet, visible, near infrared, far infrared, microwave, radio wave, etc.). For example, the solar mirror 1 may have a reflectance of visible light with a wavelength of 550 nm of at least 85%, for example at least 90%, for example at least 95%.

In the embodiment shown in FIG. 1A, the sun mirror 1 includes a substrate or layer 12 with a first main surface 14, that is, an external main surface, and an opposite second main surface 16, that is, an internal main surface. In the following discussion, the first main surface 14 faces the incident radiation, and the second surface 16 faces the opposite direction of the incident radiation. An optional base layer 102 may be created over at least a portion of one primary surface, such as a second primary surface 16. In the non-limiting embodiment shown, a primary reflective coating 22 is formed over at least a portion of the second primary surface 16, for example, over at least part of the base layer 102, if any. A protective coating 50 is formed over at least a portion of the primary reflective coating 22. Although in the illustrated embodiment, coatings are formed over the second main surface 16, it is clear that at least some coatings may alternatively form on the first main surface 14.

In the widespread practice of the invention, layer 12 may include any desired material having any desired characteristics. For example, layer 12 may be transparent or translucent for visible radiation. The term “transparent” means that the transmission is greater than 0% and up to 100% in the desired wavelength range, such as visible radiation. Alternatively, the layer 12 may be translucent. The term “translucent” means that the transmission of electromagnetic radiation (eg, visible radiation) is possible due to the diffusion or scattering of this radiation. Examples of suitable materials for layer 12 include (but are not limited to) thermoplastic, thermoset or elastomeric polymeric materials, glass, ceramics and metals or metal alloys, combinations thereof, compositions or mixtures thereof. Specific examples of suitable materials include, but are not limited to, plastic backing layers (such as acrylic polymers, e.g. polyacrylates; polyalkyl methacrylates, such as polymethyl methacrylates, polymethacrylates, polypropyl methacrylates, and the like; polyurethanes; polycarbonates; polyalkyl terephthalates, such as polyethylene terephthalate (PET, polypropylene terephthalates, polybutylene terephthalates and the like; polymers containing polysiloxanes; or copolymers of any monomers to produce polymers or any mixtures thereof); ceramic base layers; glass base layers; or mixtures or combinations of any of the above materials. For example, layer 12 may include conventional soda-lime silicate glass, borosilicate glass, or lead glass. Glass may be light. The term “light glass” means unpainted or colorless glass. Alternatively, the glass may be tinted in one way or another. The glass may be tempered or heat treated glass. As used herein, the term “heat treated” means a tempered, curved, heat strengthened, or laminated coating. Glass can be of any type, such as traditional polished glass and can have any composition, any optical properties, for example, any degree of transmission of visible light, ultraviolet, infrared and / or all solar radiation. For example, layer 12 may be light polished glass or may be tinted or colored glass. Without limiting the present invention, examples of glasses suitable for layer 12 are described in US Pat. Nos. 4,746,347; 4,792,536; 5,030,593; 5,030,594; 5,240,886; 5,385,872; and 5393593. Layer 12 may have any desired dimensions, for example, length, width, shape or thickness. In one embodiment, the first layer 12 may have a thickness greater than 0 and up to 10 mm, such a thickness as 1 mm to 10 m, for example 1 mm to 5 mm, for example, a thickness less than 4 mm, for example a thickness of 3 mm to 3.5 mm, for example, a thickness of 3.2 mm. In addition, layer 12 may have any desired shape, such as flat, curved, parabolic or the like. In addition, when the primary reflective layer (s) 22 is located on the second main surface 16 of the product, the layer 12 may contain one or more materials that have low absorption of electromagnetic radiation in the region (s) of the electromagnetic spectrum in which reflection is required.

In one non-limiting embodiment, layer 12 may have a high degree of transmittance of visible radiation at a standard wavelength of 550 nanometers (nm) and a standard thickness of 3.2 mm. The term “high transmittance of visible radiation” means a transmittance of visible radiation at 550 nm greater than or equal to 85%, such as greater than or equal to 87%, such as greater than or equal to 90%, such as greater than or equal to 91%, such as exceeding or equal to 92%, such as greater than or equal to 93%, such as greater than or equal to 95%, with a standard layer thickness of 3.2 mm. Glasses especially used in practicing the invention are disclosed in US Pat. Nos. 5,030,593 and 5,030,594. Non-limiting examples of glasses that can be used in carrying out the invention include (but are not limited to) glasses of the following brands: Starphire®, Solarphire®, Solarphire® PV, Solargreen ®, Solextra®, GL-20®, GL-35 ^TM , Solarbronze®, CLEAR, Solargray®, which are all commercially available from PPG Industries Inc. of Pittsburgh, Pennsylvania.

The base layer 102 may provide a stronger or more reliable interface between the layer 12 and the primary reflective coating 22. The base layer 102 may contain one or more materials selected so that the interface between the base layer 102 and the primary reflective coating 22 has a greater mechanical chemical and / or environmental stability than the interface between the layer 12 and the primary reflective layer 22. In addition, the base layer 102 can serve as a diffusion barrier for the exchange of elements between a layer 12 and a primary reflective coating 22 (such as the migration of sodium from the glass base layer to the overlying coating (s) or the migration of metal, for example silver from the primary reflective coating 22 into glass), which could especially occur as a result of processing the coated product with elevated temperature, for example, for bending or thermal hardening. Additionally or alternatively, the base layer 102 may provide a smoother or flatter surface on which an overlying coating will be deposited, such as a primary reflective coating 22. Examples of materials suitable for the base layer 102 include (but not limited to) inorganic materials such as ( but not limited to, low absorption transparent dielectrics, such as metal oxides or combinations thereof, compositions or mixtures of metal oxides. Examples of suitable metal oxides include alumina, titanium dioxide, zirconia, zinc oxide, zinc stannate, tin oxide, mixtures thereof or combinations thereof. Other examples for the base layer 102 include one or more layers of silicon dioxide and / or silicon nitride. In one non-limiting embodiment, the base layer 102 comprises titanium dioxide. The base layer 102 may have any composition or thickness to obtain a product with sufficient functionality (for example, mechanical, chemical, passivating, leveling, adhesive, with the property of a diffusion barrier, with increased environmental durability, optical functionality). In one particular embodiment, where the base layer 102 is titanium dioxide, the base layer 102 has a thickness in the range from 0.1 nm to 5 nm, such as from 0.1 nm to 3 nm, such as from 0.5 nm to 3 nm, such as 1 nm to 3 nm, such as 0.5 nm to 2 nm, such as 1 nm to 2 nm, such as 1.5 nm to 2 nm, such as 1.8 nm.

A primary reflective coating 22 is formed over at least a portion of the second main surface 16, for example over at least a portion of the base layer 102, if any. The primary reflective coating 22 comprises one or more inorganic or organic dielectrics, metals or semiconductors selected to reflect one or more parts of the electromagnetic spectrum, such as one or more parts in the range of electromagnetic solar radiation. In one non-limiting embodiment, the primary reflective coating 22 comprises one or more metallic films or layers reflecting radiation. Examples of suitable reflective metals include, but are not limited to, platinum, iridium, osmium, palladium, aluminum, gold, copper, silver, or mixtures, alloys, or combinations thereof. In one non-limiting embodiment, the primary reflective coating 22 comprises a silver metal layer having a thickness in the range of 50 nm to 500 nm, such as 50 nm to 300 nm, such as 60 nm to 400 nm, such as 60 nm to 300 nm, such as 70 nm to 300 nm, such as 80 nm to 200 nm, such as 80 nm to 150 nm, such as 90 nm to 150 nm, such as 90 nm to 140 nm, such as from 90 nm to 130 nm, such as from 100 nm to 130 nm, such as from 120 nm to 130 nm. In one separate, non-limiting embodiment, the primary reflective coating 22 comprises metallic silver and has a thickness of at least 50 nm, such as at least 60 nm, such as at least 70 nm, such as at least at least 80 nm (for example, in the range from 70 nm to 90 nm). The primary reflective coating 22 may be deposited to such a thickness that the article 1 has any specific required level of reflectivity in the range of electromagnetic radiation that you want to reflect. The primary reflective coating 22 may be deposited to a thickness sufficient so that the primary coating 22 is opaque in the desired wavelength range, such as visible radiation. The primary reflective coating 22 may be suitable for reflecting visible and solar infrared radiation. In one specific, non-limiting embodiment, the primary reflective coating 22 is deposited using a conventional spraying process, which is described in more detail below. In another non-limiting embodiment, the primary reflective coating 22 may comprise a “strong reflector” containing a plurality of alternating materials with a high and low refractive index.

The protective coating 50 helps to protect the underlying layers, such as the primary reflective layer 22, from mechanical and chemical influences during production, transportation, handling, processing and / or during the life of the mirror under operating conditions. In addition, the protective coating 50 helps protect the underlying layers from the ingress of liquid water, water vapor and other atmospheric pollutants (solid, liquid or gaseous). The protective coating 50 may be an oxygen impermeable coating layer that prevents or reduces the flow of oxygen from the environment to the underlying layers during subsequent processing, such as, for example, heating or bending. The protective coating 50 may be made of any desired material or mixture of materials, such as (but not limited to) one or more inorganic materials. In one embodiment, the protective coating 50 may include a layer containing one or more metal oxide materials, such as (but not limited to) aluminum, silicon oxides, or mixtures thereof. For example, the protective coating 50 may be the only coating layer having a composition in the range from 0 wt.% To 100 wt.% Alumina and / or from 100 wt.% To 0 wt.% Silicon dioxide, such as from 1 wt.% up to 99 wt.% alumina and from 99 wt.% to 1 wt.% silicon dioxide, such as from 5 wt.% to 95 wt.% alumina and from 95 wt.% to 5 wt.% silica, such as from 10 wt.% to 90 wt.% alumina and from 90 wt.% to 10 wt.% silicon dioxide, such as from 15 wt.% to 90 wt.% alumina and from 85 wt.% to 10 wt. % silica, such as from 50 wt.% to 75 wt.% alumina inium and from 50 wt.% to 25 wt.% silicon dioxide, such as from 50 wt.% to 70 wt.% alumina and from 50 wt.% to 30 wt.% silicon dioxide, such as from 35 wt.% up to 100 wt.% alumina and from 65 wt.% to 0 wt.% silicon dioxide, for example, from 70 wt.% to 90 wt.% alumina and from 30 wt.% to 10 wt.% silicon dioxide, for example , from 75 wt.% to 85 wt.% alumina and from 25 wt.% to 15 wt.% silicon dioxide, for example 88 wt.% alumina and 12 wt.% silicon dioxide, for example, from 65 wt.% up to 75 wt.% alumina and from 35 wt.% up to 25 wt.% silicon dioxide, for example, 70 wt.% alumina Nia and 30 wt.% silica, e.g., 60 wt.% to less than 75 wt.% alumina and greater than 25 wt.% to 40 wt.% silica. In one specific, non-limiting embodiment of the invention, the protective coating 50 contains from 40 wt.% To 15 wt.% Alumina and from 60 wt.% To 85 wt.% Silicon dioxide, for example, 85 wt.% Silicon dioxide and 15 wt. % alumina. Other materials may also be present, such as aluminum, chromium, hafnium, yttrium, nickel, boron, phosphorus, titanium, zirconium and / or their oxides, in order to control the refractive index of the protective coating 50. In one non-limiting embodiment, the refractive index of the protective coating 50 may be in the range from 1 to 3, such as from 1 to 2, such as from 1.4 to 2, such as from 1.4 to 1.8.

In one non-limiting embodiment, the protective coating 50 comprises a combination of silica and alumina. The protective coating 50 can be sprayed from two cathodes (for example, one silicon and the other aluminum) or from a single cathode containing silicon and aluminum. The composition of this oxide silicon / aluminum protective coating 50 can be represented as Si _x Al _1-x O _{1.5 + x / 2} , where x can vary from greater than 0 to less than 1. In one specific, non-limiting embodiment, the protective coating 50 may be a silicon oxide / aluminum coating (Si _x Al _1-x O _{1.5 + x / 2} ) having a thickness in the range of 5 nm to 5000 nm, such as 5 nm to 1000 nm, such as 10 nm up to 100 nm, for example, from 10 nm to 50 nm, such as from 10 nm to 40 nm, such as from 20 nm to 30 nm, such as 25 nm. In addition, the protective coating 50 may have a variable thickness. The term “variable thickness” means that the thickness of the protective coating 50 may vary in a given area unit, for example, the protective coating 50 may have large and small sections or areas. In another non-limiting embodiment, the protective coating 50 comprises a silicon / aluminum oxide coating or a mixture of silica and alumina, such as 85 wt.% Silica and 15 wt.% Alumina, and has a thickness in the range of 10 nm to 500 nm, such as 20 nm to 300 nm, such as 50 nm to 300 nm, for example 50 nm to 200 nm, such as 50 nm to 150 nm, such as 50 nm to 120 nm, such as 75 nm up to 120 nm, such as from 75 nm to 100 nm. In a specific, non-limiting embodiment, the protective coating 50 may have a thickness of at least 50 nm, such as at least 75 nm, such as at least 100 nm, such as at least 110 nm, such as at least 120 nm, such as at least 150 nm, such as at least 200 nm.

In another non-limiting embodiment, the protective coating 50 comprises a silicon dioxide layer having a thickness in the range of 10 nm to 100 nm, such as 10 nm to 80 nm, such as 20 nm to 80 nm, such as 30 nm to 70 nm such as from 40 nm to 60 nm, such as 50 nm. In a further, non-limiting embodiment, the protective coating 50 comprises a silicon dioxide layer having a thickness in the range of 10 nm to 500 nm, such as 10 nm to 400 nm, such as 20 nm to 300 nm, such as 50 nm to 200 nm, such as from 75 nm to 150 nm, such as from 75 nm to 120 nm.

In another non-limiting embodiment, the protective coating 50 may comprise a multilayer structure, for example, a first layer with at least one second layer formed over the first layer. In one specific, non-limiting embodiment, the first layer may comprise alumina or a mixture or alloy containing alumina and silica. For example, the first layer may comprise a silica / alumina mixture having more than 5 wt.% Alumina, for example, more than 10 wt.% Alumina, for example, more than 15 wt.% Alumina, for example, more than 30 wt.% alumina, for example, more than 40 wt.% alumina, for example from 50 wt.% to 70 wt.% alumina, for example, in the range from 70 wt.% to 100 wt.% alumina and from 30 wt.% up to 0 wt.% silicon dioxide, for example, more than 90 wt.% alumina, for example, more than 95 wt.% alumina. In one non-limiting embodiment, the first layer consists entirely or almost entirely of alumina. In one non-limiting embodiment, the first layer may have a thickness in the range of more than 0 nm to 1 μm, such as 5 nm to 10 nm, such as 10 nm to 25 nm, such as 10 nm to 15 nm. The second layer may comprise silica or a mixture or alloy containing silica and alumina. For example, the second layer may contain a mixture of silicon dioxide / alumina having more than 40 wt.% Silicon dioxide, for example, more than 50 wt.% Silicon dioxide, for example, more than 60 wt.% Silicon dioxide, for example, more than 70 wt.% silicon dioxide, for example, more than 80 wt.% silicon dioxide, such as in the range from 80 wt.% to 90 wt.% silicon dioxide and from 10 wt.% to 20 wt.% alumina, for example 85 wt.% silicon dioxide and 15 wt.% alumina. In one non-limiting embodiment, the second layer may have a thickness in the range of from more than 0 nm to 2 μm, such as 5 nm to 500 nm, such as 5 nm to 200 nm, such as 10 nm to 100 nm, such as from 30 nm to 50 nm, such as from 35 nm to 40 nm. In another, non-limiting embodiment, the second layer may have a thickness in the range of more than 0 nm to 1 μm, such as 5 nm to 10 nm, such as 10 nm to 25 nm, such as 10 nm to 15 nm. In another, non-limiting embodiment, the protective coating 50 may be a double layer formed from a first layer containing metal oxide (for example, a first layer containing silicon dioxide and / or alumina) formed over another layer containing metal oxide (for example, a second a layer containing silicon dioxide and / or alumina). The individual layers of the multilayer protective coating may have any desired thickness. Non-limiting examples of suitable protective coatings are described, for example, in US patent No. 10/007382; 10/133805; 10/397001; 10/422094; 10/422095; and 10/422096.

As discussed above, a reflective article of the invention may include one or more optional additional films, layers, coatings, or structures. Additional reflective articles of the invention will now be described with such additional structures included. However, it should be understood that the described specific optional structures or coatings are not limited to the particular embodiments shown, and furthermore, these structures can be used interchangeably in any of the embodiments of the invention.

Another non-limiting reflective article including features of the invention is shown in FIG. 1B as a sun mirror 3. In this embodiment, shown in FIG. 1B, the sun mirror 3 includes a layer 12 with a first main surface 14, that is, the outer main surface, and the opposite second main surface 16, that is, the inner main surface, as described above. An optional base layer 102 may be applied over at least a portion of one of the major surfaces, such as a second major surface 16. A primary reflective coating 22 is formed over at least a portion of the second major surface 16, for example over at least parts of the base layer 102, if any. One or more optional, corrosion resistant or anti-corrosion coatings 104 may be applied, for example, over at least a portion of the primary reflective coating 22. Primer film 106 may be applied over or below at least a portion of the anti-corrosion coating 104. The top layer 40 may be provided over at least a portion of the anti-corrosion coating 104, for example over at least a portion of the primer film 106. A protective coating 50 may be provided over at least h the top layer 40. An optional sealing structure 24 may be applied over at least a portion of the protective coating 50. Although only one anti-corrosion coating 104 is shown, the article may have a plurality of anti-corrosion coatings 104 and a plurality of primer films 106 or higher and / or lower anti-corrosion coating 104.

Layer 12, base layer 102, primary reflective coating 22, and protective coating 50 may be as described above. However, in this embodiment, the reflective article 3 also contains other layers having different functions.

For example, anti-corrosion coating 104 may provide various benefits, such as corrosion suppression and UV shielding. In addition, the anti-corrosion coating 104 may provide some reflection of electromagnetic energy, which may allow the use of a thinner primary reflective layer 22. In addition, the anti-corrosion coating 104 may provide mechanical and / or chemical protection for the underlying coating layers. The anticorrosion coating 104 may be applied below, above, or between one or more coating layers, for example, primary reflective coating (s) 22 or topcoat 40 (described below). Alternatively or in addition, the anti-corrosion coating 104 may be applied below, above, or between one or more layers of the protective coating 50. It is believed that the anti-corrosion coating 104 increases the corrosion resistance of the underlying coatings and / or increases the reflectivity of the solar mirror 3 for visible radiation , and / or can block or reduce the transmission of UV radiation. Examples of suitable materials for anti-corrosion coating 104 include (but are not limited to) elemental metals and alloys of two or more metal elements that are in groups 2-16 of the periodic table of elements, including (but not limited to) nickel and nickel-containing alloys, iron alloys and iron-containing alloys such as stainless steels, aluminum and aluminum alloys, copper and copper alloys, chromium and chromium alloys, titanium and titanium alloys, brass such as Naval brass (Cu, Zn and Sn alloys), and miralteian brass (Zn, Sn and Cu alloy) and aluminum brass (Cu, Zn and Al alloy), cobalt and cobalt-containing alloys, such as cobalt and chromium alloys, zinc and zinc-containing alloys, tin and tin-containing alloys, zirconium and zirconium-containing alloys, and molybdenum-containing alloys, tungsten and tungsten-containing alloys, niobium and niobium-containing alloys, indium and indium-containing alloys, lead and lead-containing alloys, bismuth and bismuth-containing alloys. Specific, non-limiting embodiments of the invention include corrosion-resistant metals and metal alloys, including but not limited to nickel and nickel-containing alloys such as Nickel 200, Inconel® alloys such as Inconel 600 and Inconel 625, stainless steels such as stainless steel 304 and 316 stainless steel, Monel® alloys such as Monel 400, Hastelloy® alloys, cobalt and cobalt containing alloys such as Stellite® alloys, Inco alloys such as Inco C-276 alloy and Inco 020 alloy, Incoloy® alloys such as Incoloy 800 and Incoloy 825, copper and copper alloys such as brass, special naval brass (approximately 59% copper, 40% zinc and 1% tin) and admiralty brass (approximately 69% copper, 30% zinc, 1% tin), silicon and silicon alloys, titanium and titanium alloys, aluminum and aluminum alloys, such as aluminum 6061. If there is an anti-corrosion coating (s) 104, it can have any desired thickness. In some non-limiting embodiments, anti-corrosion coatings 104 may have a thickness in the range (but not limited to) from 1 nm to 500 nm, such as from 1 nm to 400 nm, such as from 1 nm to 300 nm, such as from 1 nm up to 200 nm, such as from 1 nm to 100 nm, such as from 10 nm to 100 nm, such as from 20 nm to 100 nm, such as from 30 nm to 100 nm, such as from 40 nm to 100 nm, such as 50 nm to 100 nm, such as 20 nm to 40 nm, such as 30 nm to 40 nm, such as 30 nm to 35 nm. In other non-limiting embodiments, the implementation of the anti-corrosion coating (s) 104 may have a thickness of at least 10 nm, such as at least 20 nm, such as at least 30 nm, such as at least 40 nm, such as at least 50 nm, such as at least 100 nm, such as at least 200 nm. In one specific, non-limiting embodiment, the anti-corrosion coating (s) 104 contains Inconel and may have a thickness in the range of 10 nm to 100 nm, such as 10 nm to 80 nm, such as 15 nm to 50 nm, such as 20 nm to 40 nm, such as from 30 nm to 40 nm, such as from 30 nm to 35 nm.

An optional primer layer 106 may be formed above and / or below the anti-corrosion coating (s) 104. This primer layer 106 has one or both of the following functions: (a) a chemical getter for oxygen or other chemical particles (either endogenous or exogenous for the product) in order to accelerate their interaction with the primer layer (s), in comparison with the primary reflective coating 22, and / or (b) a physical diffusion barrier in order to prevent the ingress and influence of chemical particles (not required but due to a chemical reaction) to the primary reflective coating 22. In one specific embodiment, the optional primer layer (s) 106 may contain a metal or metal alloy that has a strong affinity for oxygen and / or the product of a chemical reaction of a metal or metal alloy with oxygen . The optional primer layer (s) 106 may also contain materials that create a diffusion barrier to prevent diffusion of molecular or atomic oxygen, water vapor, or other gaseous particles, and their subsequent interaction with the primary reflective coating 22. In one specific embodiment, the primer layer 106 contains titanium, titanium oxide, or a mixture / combination thereof. In one particular embodiment, primer 106 may have a thickness in the range of 0.1 to 10 nm, such as 0.5 to 5 nm, such as 0.5 to 4 nm, such as 0.5 to 2 nm such as from 1 nm to 2 nm.

The topcoat 40 is formed over at least a portion of the primary reflective coating 22, for example, over at least a portion of the anti-corrosion layer 104, for example, over at least a portion of the primer 106. The topcoat 40 may comprise one or more layers, for example, one or more dielectric layers, such as one or more metal oxides, nitrides, oxynitrides, borides, fluorides or carbides. In one non-limiting embodiment, topcoat 40 may be a single layer containing zinc and tin oxide, such as zinc stannate. In another specific, non-limiting embodiment, topcoat 40 may comprise a multi-film structure, as described below in connection with FIG. 1C. However, it should be understood that the invention is not limited to oxide coatings. In one non-limiting embodiment, topcoat 40 comprises zinc stannate. The topcoat may have a thickness of at least 10 nm, such as at least 20 nm, such as at least 50 nm, such as at least 75 nm, such as at least 100 nm, such as at least 150 nm, such as at least 200 nm. In one specific, non-limiting embodiment, the topcoat may have a thickness in the range of 5 nm to 500 nm, such as 10 nm to 500 nm, such as 50 nm to 500 nm, for example, 50 nm to 300 nm, such as from 100 nm to 250 nm, such as from 100 nm to 200 nm, such as from 120 nm to 165 nm, such as from 110 nm to 165 nm. Generally, the thicker the topcoat, the greater the protection provided for the underlying coats.

An optional sealing structure 24 may be formed on top of and / or around at least a portion of the coating layer 12 as described above. In one non-limiting embodiment, the sealing structure 24 is formed at least partially by the sealing material 92. Suitable sealing materials 92 may include polymeric materials, inorganic materials or composite materials, combinations thereof, combinations, mixtures and alloys. When a significant portion or all of the sealing material 92 contains a polymer material, this sealing material 92 can be deposited by any conventional method, such as (but not limited to) brush coating, roller coating, spray coating, spray coating, dipping coating, centrifugal coating , knife edge coating, screen printing, pouring coating, electrocoating (aka electrodeposition) and powder coating. Suitable polymeric sealing materials 92 include, but are not limited to, thermoplastic, thermosetting polymers, elastomers, and thermoplastic elastomers formed by addition or condensation polymerization with or without crosslinking, and copolymers and compositions, combinations, mixtures, combinations and alloys thereof. However, in sealing materials containing polymeric materials, various additives and fillers can be used, including initiators, photoinitiators, plasticizers, stabilizers, fuses, biocides, leveling agents, flow improvers, antioxidants, UV absorbers, surfactants, dyes, pigments and inorganic or organic fillers. Possible all-polymer sealing materials may include (but not limited to) polyacrylates, polyalkides, polyacrylonitriles, polyesters, polyfluorocarbons, polyvinyls, polyureas, polymelamines and polycarbonates. For example, the sealing structure 24 may include acrylate-based coatings, urethane-based coatings, fluoropolymer and / or chlorofluoropolymer coatings (e.g., polyfluoroethylene, polychlorotrifluoroethylene and others), polyvinylidene chloride-based coatings, ethylene vinyl alcohol-based coatings, polyacrylonitrile-based coatings, coatings based on cyclic olefin polymers or based on copolymers, composite inorganic / organic coatings: organic polymer matrices with one or more neo by chemical phases (e.g. ceramic-like silica and alumina) dispersed either uniformly or unevenly inside the plasma sprayed inorganic coatings: ceramics (e.g. silicon dioxide, alumina, silicon nitride, titanium boride, titanium carbide, boron nitride, carbide silicon) and metal alloys (aluminum, titanium, Inconel-type nickel-based alloys, stainless steel-type iron alloys), vulcanized butadiene-based coatings (such as synthetic rubbers, sulfur crosslinked), UV curable teachings polysiloxane coatings, laminates comprising polymer interlayers (e.g., intermediate layers of ethylene vinyl acetate or polyvinylidene chloride) and a glass base plate. In one, non-limiting embodiment, the polymeric material does not contain heavy metals such as lead. For sealing materials consisting entirely of inorganic materials, suitable materials include (but are not limited to) metals, metal alloys, ceramics, and composite materials, or combinations thereof. Examples of suitable deposition methods for such inorganic sealing materials include physical vapor deposition (e.g., sputtering, electron beam evaporation, thermal evaporation, cathodic arc deposition, plasma sputtering deposition, flame sputtering deposition, pyrolytic deposition deposition, chemical vapor deposition) vapor (e.g., thermal chemical vapor deposition (CVD), plasma induced / enhanced CVD), sol-gel deposition, other wet e chemical processes (e.g. ceramic enamels), and combinations thereof. In addition, the sealing structure 24 may contain polymeric as well as inorganic materials in combination.

Specific coatings suitable for seal structure 24 include, but are not limited to, the Corabond® coating family (such as Corabond® HC7707 coatings) commercially available from PPG Industries, Inc. of Pittsburgh, Pennsylvania, Ferro GAL-1875 Etch Ceramic Enamel, Cosmichrome® Coating (commercially available from Gold Touch, Inc.), Sureguard® Mirror-Coated Coating (commercially available from Spraylat Corporation), EcoBrite® Ink Coating (industrial available from PPG Industries, Inc), PRC 4429 and PRC 4400 coatings, commercially available from PRC DeSoto, and Spraylat Lacryl Series 700 or 800 coatings (available from Spraylat Corporation). Alternatively, the sealing structure 24 may be metal, such as is formed from one or more metal layers, such as those described above in connection with the anti-corrosion coating 104, formed over the second reflective coating 22 with an optional polymer material formed over the metal layer ( layers). Further examples of non-polymer / inorganic sealing materials include ceramic enamels, sol-gel ceramic coatings, ceramic or metal flame spray coatings, ceramic or metal plasma spray coatings, and ceramic or metal coatings by cathodic arc discharge. In one specific, non-limiting embodiment, the sealing structure 24 may be a multilayer structure, such as a two-layer coating having a low lead or no lead base layer and a low or no lead top layer.

An additional, non-limiting solar mirror 10 including features of the invention is shown in FIG. 1C. In the embodiment shown in FIG. 1C, the sun mirror 10 includes a first layer 12 with a first main surface 14, that is, an external main surface, and an opposite second main surface 16, that is, an internal main surface, as described above. In one non-limiting embodiment, an optional secondary reflective coating 20 is formed over at least a portion of the inner surface 16. In another non-limiting embodiment, an optional secondary reflective coating 20 may be formed over at least a portion of the outer main surface 14. Primary reflective coating 22 formed over at least part of the second main surface 16, for example, over at least part of the secondary reflective coating 20, if any an original reflective coating 20, and on the second main surface 16. An anti-corrosion coating 104 may be formed over at least a portion of the primary reflective coating 22. An upper coating 40 may be formed over at least a portion of the anti-corrosion coating 104. A protective coating 50 may be formed on top of at least a portion of the topcoat 40. The mirror 10 may also include a sealing structure 24.

An optional secondary reflective coating 20, if present, can perform one or more functions in the sun mirror 10. In one non-limiting embodiment, the secondary reflective coating 20 can be selected to enhance the overall reflection of electromagnetic radiation from the reflective article in a specific region or range of electromagnetic radiation . The secondary reflective coating 20 may be selected or constructed to reflect electromagnetic radiation in one or more parts of the electromagnetic spectrum (e.g., visible, infrared, ultraviolet). In one non-limiting embodiment, the secondary reflective coating 20 may be selected to enhance reflection of short-wavelength radiation, such as radiation with a wavelength of less than 600 nm, such as less than 550 nm, such as in the range from 400 nm to 550 nm. Alternatively, the secondary reflective coating 20 can be adjusted, for example, by varying its thickness, to reflect UV radiation. Secondary reflective coating 20 may comprise one or more layers of reflective material, such as one or more layers of metal oxide materials. In one specific, non-limiting embodiment, the secondary reflective coating 20 comprises alternating layers of material with a relatively high refractive index and material with a relatively low refractive index. A material with a "high" refractive index is any material having a refractive index higher than that of a material with a "low" refractive index. In one non-limiting embodiment, the low refractive index material is a material having a refractive index of less than or equal to 1.75. Non-limiting examples of low refractive index materials include silica, alumina, fluorides (such as magnesium and calcium fluoride) and alloys, mixtures or combinations thereof. In one non-limiting embodiment, the high refractive index material has a refractive index of greater than 1.75. Non-limiting examples of such materials include titanium dioxide, zirconia, zinc otannate, silicon nitride, zinc oxide, tin oxide zinc, niobium oxide, tantalum oxide and their alloys, mixtures and combinations. For example, the secondary reflective coating 20 may be (but not limited to the present invention) a multilayer coating, as shown in FIG. 1C, which has a first layer 26, for example a first dielectric layer, and a second layer 28, for example a second dielectric layer. In one non-limiting embodiment, the first layer 26 has a high refractive index, and the second layer 28 has a low refractive index. In one non-limiting embodiment, the first layer 26 contains titanium dioxide and the second layer 28 contains silicon dioxide. In one specific, non-limiting embodiment, the first layer, for example titanium dioxide, has a thickness in the range from 15 nm to 35 nm, for example from 20 nm to 30 nm, such as from 22 nm to 27 nm, such as 25 nm. The second layer, for example silicon dioxide, may have a thickness in the range from 30 nm to 60 nm, for example from 35 nm to 50 nm, such as from 40 nm to 50 nm, such as 42 nm. It should be understood that the materials of the secondary reflective coating 20 are not limited to metal oxides. Any materials may be used, such as (but not limited to) oxides, nitrides, oxynitrides, fluorides, etc.

In the non-limiting embodiment shown in FIG. 1C, an optional adhesive layer 30 may be provided between the secondary reflective coating 20 and the primary reflective coating 22. The adhesive layer 30 may be any layer that enhances adhesion between the secondary and primary reflective coatings 20, 22 or improves the mechanical and / or chemical durability of the secondary or primary reflective coatings 20, 22. The adhesive layer 30 may contain at least one material selected from dielectrics, a semiconductor c, polymers, organic compounds, layers of metal or metal alloys. In one non-limiting embodiment, the adhesive layer 30 comprises at least one material selected from oxides, nitrides, or oxynitrides of zinc, tin, titanium, or combinations thereof, such as (but not limited to) zinc oxide, titanium dioxide or zinc oxide / tin, such as zinc stannate. For example, the adhesive layer 30 may have a thickness of less than or equal to 5 nm, such as less than or equal to 4 nm, such as less than or equal to 3 nm, such as less than or equal to 2 nm, such as less than or equal to 1 nm

In the illustrated embodiment shown in FIG. 1C, a topcoat 40 is formed over at least a portion of the primary reflective coating 22. The topcoat 40 may be as described above. In one specific, non-limiting embodiment, the topcoat may comprise one or more layers, for example, one or more dielectric layers, for example, one or more metal oxides, nitrides, oxynitrides, borides, fluorides or carbides. In one specific, non-limiting embodiment, the topcoat 40 comprises a multi-film structure having a first film 42, for example a metal oxide film, a second film 44, for example a metal alloy oxide or oxide mixture film, and optionally a third film 46, for example a metal oxide film. However, it should be understood that the invention is not limited to oxide coatings and that other coatings such as nitrides or oxynitrides can be used (but not limited to). In one non-limiting embodiment, topcoat 40 may comprise zinc oxide or zinc / tin oxide, such as zinc stannate, and may have a thickness in the range of 1 nm to 500 nm, such as 5 nm to 500 nm, such as 10 nm up to 500 nm, such as from 50 nm to 500 nm, for example from 50 nm to 300 nm, such as from 100 nm to 250 nm, such as from 100 nm to 200 nm, such as from 120 nm to 165 nm.

In one non-limiting embodiment, the first film 42 may be a zinc-containing film, such as zinc oxide. A zinc oxide film can be deposited from a zinc cathode into which other materials are introduced in order to improve the conductivity and atomization characteristics of the cathode. For example, the zinc cathode may contain a small amount (for example, 10 wt.% Or less, for example, from 0 wt.% To 5 wt.%) Of the conductive material, such as tin, in order to improve the atomization characteristics of the cathode. In this case, the resulting zinc oxide film will include a small fraction of tin oxide, for example from 0 to 10 wt.% Tin oxide, for example from 0 to 5 wt.% Tin oxide. A coating layer deposited from a zinc cathode containing 10% by weight or less of tin is referred to in the present invention as a “zinc oxide” layer, although a small amount of tin (for example, 10% by weight) may be present. It is believed that from a small amount of tin in the cathode, a small amount of tin oxide is formed in the film, which mainly contains zinc oxide. In one non-limiting embodiment, the first zinc oxide film 42 contains 90 wt.% Zinc and 10 wt.% Tin and has a thickness in the range of 1 nm to 200 nm, such as 1 nm to 150 nm, such as 1 nm to 100 nm, such as 1 nm to 50 nm, such as 1 nm to 25 nm, such as 1 nm to 20 nm, such as 1 nm to 10 nm, such as 2 nm to 8 nm, such as 3 nm to 8 nm, such as 4 nm to 7 nm, such as 5 nm to 7 nm, such as 6 nm.

In one non-limiting embodiment, the second film 44 may be a zinc oxide / tin alloy film or a mixture of zinc / tin oxides. Zinc-tin alloy oxide can be obtained by vacuum deposition by magnetron sputtering of a zinc-tin cathode, which contains zinc and tin in a ratio of 10 wt.% To 90 wt.% Zinc and from 90 wt.% To 10 wt.% Tin . One suitable metal alloy oxide that may be present in the second film 44 is zinc stannate. The term “zinc stannate” means the composition of Zn _X Sn _1-X O _2-X (formula 1), where “x” ranges from more than 0 to less than 1. For example, “x” may be more than 0 and may be any fraction or decimal between more than 0 to less than 1. For example, when x = _2/3 , formula 1 is Zn _2/3 nSn _1/3 O _4/3 , which is more commonly written as “Zn ₂ SnO ₄ ". A film containing zinc stannate has one or more forms of formula 1, and its amount prevails in the film. In one non-limiting embodiment, the second zinc stannate film 44 may have a thickness in the range of 1 nm to 200 nm, such as 1 nm to 150 nm, such as 1 nm to 100 nm, such as 1 nm to 50 nm, such as 1 nm to 25 nm, such as 1 nm to 20 nm, such as 5 nm to 15 nm, such as 6 nm to 14 nm, such as 8 nm to 14 nm, such as 10 nm to 14 nm, such as from 11 nm to 13 nm, such as 12 nm.

In one non-limiting embodiment, the optional third film 46 may be a zinc-containing film similar to the first film 42, for example a zinc oxide film. In one non-limiting embodiment, the optional zinc oxide film 46 has a thickness in the range of 1 nm to 200 nm, such as 1 nm to 150 nm, such as 1 nm to 100 nm, such as 1 nm to 50 nm, such as from 1 nm to 25 nm, such as from 1 nm to 10 nm, such as in the range from 2 nm to 8 nm, such as in the range from 3 nm to 8 nm, such as in the range from 4 nm to 7 nm, such as in the range from 5 nm to 7 nm, such as 6 nm.

In one non-limiting embodiment, the solar mirror 10 may have a photoactive coating 60, such as a photocatalytic and / or photohydrophilic coating, formed over at least a portion of the first surface 14. A non-limiting example of one suitable material for the photoactive coating 60 is titanium dioxide. The photoactive coating 60 may be deposited directly on the first surface 14 or on a barrier layer, such as a sodium ion diffusion barrier layer (SIDB) 64, which may be provided between the first surface 14 and the photoactive coating 60. A non-limiting example of a suitable material for the SIDB layer is silica, or alumina, or combinations thereof. Alternatively, the photoactive coating 60 can be eliminated, and only the SIDB layer is formed over the first surface 14.

Some or all of the coatings described above for the reflective products of the invention can be precipitated by any conventional method, such as (but not limited to) wet chemical methods (e.g., coating the solution from a solution, coating by chemical reduction, sol-gel chemical method, etc. .), electrochemical methods (e.g. electroplating / electrodeposition), spray deposition (e.g. magnetron sputtering vapor deposition (MSVD)), sputtering (e.g. thermal or electron beam sputtering ), chemical vapor deposition (CVD), jet pyrolysis, flame spraying or plasma spraying. In one non-limiting embodiment, some or all of the coatings may be deposited by MSVD. Examples of MSVD devices and coating methods are well known to those skilled in the art and are described, for example, in US Pat. Nos. 4,379,040; 4,861,669; 4,898,789; 4,898,790; 4,900,633; 4920006; 4,938,857; 5,328,768; and 5492750. For example, the primary reflective coating 22 can be applied by wet chemical methods (for example, applying "wet silver" - by deposition of silver from a solution of silver nitrate), if necessary. In one non-limiting embodiment, one or more layers of the secondary reflective coating 20 can be applied by conventional CVD methods, for example, on a polished glass tape when the tape is in a tin bath. Then, the primary reflective coating 22 and one or more layers of the upper coating 40 can be applied using another process, such as MSVD. Alternatively, all coatings may be applied in a similar manner, such as MSVD. It is believed that the application of at least some coatings by spraying has advantages over many other methods. For example, a large number of materials can be deposited in a single vacuum chamber. In addition, it can be expected that spray deposition will produce layers with a higher chemical purity than traditional wet chemical methods. Moreover, when spraying, there is no liquid waste stream, which is formed in the case of wet chemical methods, and also provides easy deposition of other metals. In addition, spraying provides the application of inorganic oxides, which can be used as adhesive layers, chemical barriers and mechanical protection.

The sealing structure 24 may be formed on top of and / or around at least a portion of the coating layer described above. The sealing structure 24 is not limited to the examples described above, but may include any material to protect the underlying coating materials from chemical and / or mechanical stress. For example, in the solar mirror 80 shown in FIG. 2, the sealing structure 24 includes a second layer 82 attached to the first layer 12, for example, to the protective coating 50, using the polymer layer 84. The second layer 82 may be selected from materials described above for the first layer 12, and may be the same as or different from the first layer 12. In addition, the second layer 82 is not necessarily transparent to electromagnetic radiation in any part of the electromagnetic spectrum.

The polymer layer 84 may contain any desired material and may include one or more layers. Layer (s) 84 may include thermoplastics, thermosetting plastics, elastomers and / or thermoplastic elastomers. Layer 84 may be a polymeric or plastic material, such as, for example, polyvinyl butyral, plasticized polyvinyl chloride, or multilayer thermoplastic materials, including polyethylene terephthalate, ethylene vinyl acetate (EVA), polyvinyl chloride, polyvinylidene chloride, polyacrylate, for example, polyacrylate, such as , polyesters, melamines, polyureas, polyurethanes, polyalkides, polyphenol formaldehydes, etc. Suitable materials are described (but without limitation) in US patent No. 4287107 and 37629 88. A layer 84 bonding the first and second layers together can provide energy absorption and can increase the strength of the laminated structure. In one non-limiting embodiment, the layer 84 is made of polyvinyl butyral and has a thickness in the range from 0.5 mm to 1.5 mm, such as from 0.75 mm to 0.8 mm.

In the solar mirror 90 of the invention shown in FIG. 3, a polymer sealing structure 24 may be used, formed at least in part with the sealing material 92, as described above. Sealing material 92 may be wound around at least a portion of the sides (a small portion of the surface) of the solar mirror 90, providing sealing of the edge of the product. Alternatively, a conventional edge sealant, such as (but not limited to) polyvinylidene chloride (PVDC), may be applied to the edges, that is, a small portion of the surface of the article prior to application of the sealing material.

Another solar mirror 100 of the invention is shown in FIG. The solar mirror 100 includes a first layer 12, as described above. In this embodiment, the secondary reflective coating 20 is absent. A primary reflective coating 22 may be applied over at least a portion of the second primary surface 16. In one specific embodiment, the base layer 102 is provided between the second primary surface 16 and the primary reflective coating 22. The base layer 102 may be the same as described above .

In this embodiment, the primary reflective coating 22 may be made of any of the materials described above in connection with earlier embodiments. In one specific embodiment, the primary reflective coating 22 comprises a silver metal layer having a thickness in the range of 10 nm to 500 nm, such as 50 nm to 500 nm, for example, 50 nm to 300 nm, such as 50 nm to 200 nm such as 100 nm to 200 nm, such as 100 nm to 150 nm, such as 110 nm to 140 nm, such as 120 nm to 140 nm, such as 128 nm to 132 nm. In another specific embodiment, the primary reflective coating 22 comprises a silver metal layer having a thickness in the range of 1 nm to 500 nm, such as 50 nm to 500 nm, for example 50 nm to 300 nm, such as 50 nm to 200 nm, such as 50 nm to 150 nm, such as 70 nm to 150 nm, such as 90 nm to 120 nm, such as 90 nm to 130 nm, such as 90 nm to 100 nm, such as 90 nm up to 95 nm.

Topcoat 40 may be a single layer or a multilayer structure having a first layer 110 and a second layer 112. In one specific embodiment, the first metal oxide layer 110 comprises a zinc oxide layer having a thickness in the range of 1 nm to 30 nm, such as 1 nm to 25 nm, such as 5 nm to 20 nm, such as 10 nm to 20 nm, such as 10 nm to 17 nm. The second layer 112 contains zinc stannate and has a thickness in the range from 10 nm to 100 nm, such as from 40 nm to 45 nm.

The solar mirror 100 may also include a protective coating 114, which may be the same or similar to the protective coating 50 described above. In one specific embodiment, the protective coating 114 comprises a silicon dioxide layer having a thickness in the range of 10 nm to 500 nm, such as 10 nm to 300 nm, such as 10 nm to 100 nm, such as 20 nm to 100 nm such as 30 nm to 80 nm, such as 40 nm to 60 nm, such as 50 nm to 60 nm, such as 57 nm.

Figure 5 shows a reflective product of the invention (for example, a solar mirror 1, 3, 10, 80, 90, 100) mounted on a support frame 120. The reflective product is mounted so that the first main surface 14 is facing outward. Reflective products can be mounted by any conventional method, for example using glue or by mechanically securing the product to a frame, only a few methods are mentioned. The bed 120 may be attached to the sealing structure 24, as described above. Alternatively, the sealing structure 24 may be omitted, and the bed 120 is connected to the outer layer of the coating of the coating kit, for example, with a protective coating 50. This bed 120 can be made of any desired material, such as (but not limited to) metal (such as aluminum, stainless steel, etc.) or a polymeric material such as plastic.

The invention creates products with high reflectivity, which are used in many fields, for example, in solar mirrors (but not limited to this). The reflective articles of the invention may have a hemispherical weighted integrated reflectivity of solar red-green radiation (WIRg) of at least 50%, such as at least 60%, such as at least 70%, such as at least 80%, such as at least 90%, such as at least 91%, such as at least 92%, such as at least 93%, such as at least 94%, such as at least 95%, such as in the range from 90% to 96%.

As described above and as shown in the following examples, the advantage of the reflective article of the invention over conventional wet chemical mirrors is that the reflective article of the invention can be coated and then heated to a temperature sufficient to heat it or bending the coated article (prior to applying any polymer sealing structure) without adversely affecting the reflectivity of the article. In addition, the coatings of the invention can demonstrate an improvement in spectral characteristics (i.e., an increase in reflectivity in some or all of the measured spectrum range) and an increase in the weighted integrated reflectivity of solar radiation after heating. For example, a reflective article of the invention having a base layer and / or a primary reflective coating and / or a secondary reflective coating and / or an anti-corrosion coating and / or a top coating and / or a protective coating can be heated to a temperature sufficient to bend or heat treatment of the product before applying the sealing structure. For example, the substrate and coatings can be heated to at least 300 ° F (149 ° C), for example at least 350 ° F (177 ° C), for example, at least 400 ° F (204 ° C), for example at least 500 ° F (260 ° C), for example at least 750 ° F (399 ° C), for example at least 800 ° F (427 ° C), for example at least 900 ° F (482 ° C), for example at least 1000 ° F (538 ° C), for example at least 1022 ° F (550 ° C), for example, at least 1100 ° F (593 ° C), for example at least 1200 ° F (649 ° C), for example at least 1300 ° F (704 ° C), for example, in the range from 350 ° F (177 ° C ) to 1300 ° F (704 ° C).

The invention will now be described with reference to specific examples illustrating mirrors with various structures incorporating various aspects of the invention. However, it should be understood that the invention is not limited to these specific examples.

Examples

Table 1 shows the structure of the various mirrors (samples 1-10) of the invention.

Table 2 shows the hemispherical reflectivity WIRg (weighted integrated reflectivity of solar radiation Rg) of samples 1-15 of the mirrors before and after heating. From these results it is seen that the hemispherical weighted integrated reflectivity of solar radiation by the mirrors of the invention can increase with heating. The “Softening Point” column means that coated products were placed in an oven at 1300 ° F (704 ° C) and heated (approximately 5 minutes) to the glass softening temperature (maximum coated surface temperature was about 1185 ° F (641 ° C) .

table 2 After precipitation (without heating) 30 minutes. at 350 ° F (177 ° C) Softening point Sample No. ASTM G-173-3 AM- 1.5D ISO 9050 ASTM G- 173-3AM-1,5D ISO 9050 ASTM G- 173-3AM-1,5D ISO 9050 one 92.9 92.7 93.6 93,4 93.1 92.8 2 92.6 92.4 93.5 93.3 94.2 94.1 3 not measured not measured not measured not measured not measured not measured four not measured not measured not measured not measured not measured not measured 5 92.8 92.6 93,4 93.3 93.8 93.6 6 92.8 92.6 93,4 93.3 93.9 93.8 7 92.9 92.7 93.5 93,4 93.9 93.7 8 92.9 92.7 93.5 93.3 88.5 88.1 9 92.7 92.4 93.7 93.5 94.2 94.0 10 93.1 92.9 there is no data there is no data 93.9 93.8 eleven 94.0 93.8 there is no data there is no data 95.5 95.3 12 there is no data there is no data there is no data there is no data there is no data there is no data 13 there is no data there is no data there is no data there is no data there is no data there is no data fourteen 93.7 93,4 there is no data there is no data 95.4 95.2 fifteen 94.0 93.7 there is no data there is no data 95.4 95.2

One skilled in the art will be able to readily understand that modifications to the invention can be made without departing from its spirit as set forth above in the description. Therefore, certain embodiments described in detail in the present invention are illustrative only and do not limit the scope of the invention, which is fully defined by the appended claims and any and all equivalents thereof.

Claims (15)

1. Reflective product, which includes:
a transparent substrate having a first main surface and a second main surface;
a base layer formed over at least a portion of the second main surface;
a primary reflective coating formed over at least a portion of the base layer;
an inorganic protective coating, which consists essentially of a material selected from the group consisting of silica, alumina or a mixture of silica and alumina, formed over at least a portion of the primary reflective coating;
a topcoat that contains zinc stannate formed between the primary reflective coating and the inorganic protective coating;
moreover, the base layer contains titanium dioxide with a thickness of from 1 nm to 3 nm. 2. The reflective product according to claim 1, in which the primary reflective coating is opaque in the visible region of the spectrum and contains at least one metal film. 3. The reflective product according to claim 2, in which the primary reflective coating contains at least one metal selected from platinum, iridium, osmium, palladium, aluminum, gold, copper, silver, or mixtures, alloys, or combinations thereof. 4. The reflective product according to claim 3, in which the primary reflective coating contains silver. 5. The reflective product according to claim 3, in which the primary reflective coating has a thickness in the range from 50 nm to 200 nm. 6. The reflective product according to claim 1, in which the protective coating has a thickness in the range from 75 nm to 120 nm. 7. The reflective article of claim 1, which includes a sealing structure formed over at least a portion of the protective coating. 8. The reflective article of claim 7, wherein the sealing structure includes a polymeric material. 9. The reflective product according to claim 1, comprising an anti-corrosion coating located between the primary reflective coating and the protective coating. 10. The reflective product according to claim 9, in which the anticorrosion coating contains at least one metal or metal alloy, consisting of representatives of groups 2-16 of the Periodic table of elements. 11. The reflective article of claim 1, further comprising a photoactive coating formed over at least a portion of the first main surface. 12. Reflective product, which includes:
a transparent glass substrate having a first main surface and a second main surface;
an inorganic base layer that contains at least one metal oxide selected from alumina, titanium dioxide, zirconia, zinc oxide, zinc stannate, tin oxide, or mixtures thereof, or combinations thereof, and has a thickness in the range of 0 , 1 nm to 5 nm, formed over at least a portion of the second main surface;
primary reflective coating, opaque in the visible region of the spectrum, which contains at least one metal selected from platinum, iridium, osmium, palladium, aluminum, gold, copper, silver, or mixtures, alloys, or combinations thereof, and has a thickness in the range of 50 nm to 500 nm, formed over at least a portion of the base layer;
anticorrosive coating, which contains at least one metal or metal alloy, consisting of representatives of groups 2-16 of the Periodic table of elements, and has a thickness in the range from 20 nm to 40 nm, formed over at least part of the primary reflective coating;
a topcoat that contains at least one layer that includes a material selected from metal oxides, nitrides, oxynitrides, borides, fluorides or carbides and has a thickness in the range of 5 nm to 500 nm formed over at least part of the anti-corrosion coating; and
an inorganic protective coating that includes a material selected from silica, alumina, or a mixture of silica and alumina, and has a thickness in the range of 50 nm to 500 nm, formed over at least a portion of the topcoat. 13. Reflective product, which includes:
a transparent glass substrate having a first main surface and a second main surface;
an inorganic base layer comprising a titanium dioxide layer having a thickness in the range of 1 nm to 3 nm, formed over at least a portion of the second main surface;
a primary reflective coating comprising a silver layer having a thickness in the range of 50 nm to 200 nm, formed over at least a portion of the base layer;
an anti-corrosion coating comprising a nickel-containing alloy having a thickness in the range of 20 nm to 40 nm, formed over at least a portion of the primary reflective coating;
a topcoat comprising a zinc stannate layer having a thickness in the range of 100 nm to 200 nm, formed over at least a portion of the anti-corrosion coating; and
an inorganic protective coating comprising a material selected from silica, alumina, or a mixture of silica and alumina, having a thickness in the range of 50 nm to 200 nm, formed over at least a portion of the topcoat, where the protective coating . 14. The reflective article of claim 13, which includes a sealing structure that comprises a polymer material formed over at least a portion of the protective coating. 15. Reflective product, which includes:
a transparent glass substrate having a first main surface and a second main surface;
a base layer that contains a transparent dielectric material formed over at least a portion of the second main surface;
a primary reflective coating that is opaque in the visible region of the spectrum and contains at least one metal film formed over at least a portion of the base layer;
an inorganic protective coating that includes a material selected from silica, alumina, or a mixture of silica and alumina formed over at least a portion of the primary reflective coating; and
a sealing structure that comprises a polymer material formed over at least a portion of the protective coating.

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